Phthalimidyl-azo-m-acylamido-n-substituted aniline compounds and polyester fibers dyed therewith

ABSTRACT

Monoazo compounds containing a N-substituted-3- or 4-phthalimidyl diazo component and certain m-acylamido-N-substituted aniline residue coupling components produce bright scarlet to red shades on fibers of, for example, polyester, polyamide and cellulose esters, and exhibit improved dyeability properties and good to excellent fastness to light, high pH, sublimation and crocking.

This invention relates to certain novel disperse dye azo compounds and the use thereof and, more particularly, to certain phthalimidyl-azo-aniline compounds and textiles dyed therewith.

Our novel compounds have the general formula ##STR1## wherein R is hydrogen, an organic radical having a molecular weight of not more than 200;

A is an organic acyl radical;

R¹ is hydrogen or lower alkyl;

R² individually is alkyl containing one to about eight carbon atoms; cyclohexyl; cyclohexyl substituted with lower alkyl; or lower alkyl substituted with lower alkoxy, aryl, aryloxy, cyclohexyl, cyano, lower alkanoyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, aroyloxy, lower alkylcarbamoyloxy, arylcarbamoyloxy, or a group having the formula ##STR2## wherein R⁴ individually is hydrogen, lower alkyl or aryl;

R⁵ individually is hydrogen or lower alkyl;

R⁴ and R⁵ collectively are --(CH₂)₅ -- or --CH₂ CH₂ OCH₂ CH₂ --;

A is an acyl radical;

R⁶ is hydrogen, lower alkyl, aryl, or cyclohexyl;

R⁷ is ethylene, propylene, trimethylene, o-cyclohexylene, or o-arylene, or when X is --CO--, R⁷ also can be --NHCH₂ --, --N(lower alkyl)CH₂ --, --SCH₂ --, --OCH₂ --, or --CH₂ OCH₂ --;

X is --CH₂ --, --CO--, or --SO₂ --; and

R⁸ is aryl, benzyl, cyclohexyl, 1,2,4-triazol-3-yl, or 2-benzothiazolyl;

R³ individually is hydrogen; lower alkyl; lower alkyl substituted with lower alkoxy, aryl, aryloxy, cyclohexyl, lower alkanoyloxy, lower alkoxycarbonyl or lower alkoxycarbonyloxy; allyl; or aryl; and

R² and R³ in combination is a group having the formula --CH₂ CH₂ --Y--CH₂ CH₂ -- in which Y is --CH₂ --, --O--, --S--, --SO-- or --SO₂ --.

The disperse dye azo compounds of the invention produce bright scarlet to red shades on polyester and other fibers on which the compounds exhibit good fastness and dyeability properties. Our azo compounds, in general, exhibit good to excellent fastness to light, washing and sublimation. These dyes exhibit particularly excellent light fastness on nylon (polyamide) and cellulose acetate fibers. The fastness to sublimation and dyeability properties of our novel compounds will vary moderately depending on the substituents present on the structure of formula (I). Our compounds also exhibit good to excellent stability over a pH range of 4 to 8 when applied to texturized polyester fibers at elevated pressures at 250° to 265° F. The good dyeability properties of our compounds render them fast to crocking and result in good build-up and barre coverage. The unique combination of properties possessed by our novel compounds renders them superior to the compounds disclosed in Canadian Pat. No. 776,561, French Pat. No. 1,358,145, the Indian Journal of Technology, Vol. 9, pp. 175-178, and Offenlegungsschrift No. 2,164,198.

Our novel azo compounds are synthesized by diazotizing a 3- or 4-aminophthalimide having the formula ##STR3## and coupling the resulting diazonium salt with a coupler having the formula ##STR4## according to conventional techniques. The 3-aminophthalimides in which R is hydrogen, are prepared by reacting 3-nitrophthalic anhydride with ammonia followed by the reduction of the nitro group to the amino group whereas the analogous 4-amino compounds are prepared by reacting phthalic anhydride with ammonia followed by nitration and reduction. The corresponding aminophthalimide compounds in which R is a substituent are prepared by the mentioned techniques except that a primary amine is substituted for the ammonia. Alternatively, the aminophthalimide compounds in which R is a substituent can be prepared by reacting either phthalimide or a nitrophthalimide with an alkylating agent such as an aliphatic halide. The particular substituent represented by R is, in general, not critical. However, since our novel azo compounds are disperse dye compounds, substituent R is free of water-solubilizing groups such as sulfonate and carboxylate salt groups. The primary amines from which substituent R can be derived have the formula R--NH₂ in which R is an unsubstituted or substituted aliphatic, alicyclic, aromatic or heterocyclic residue having a molecular weight of not more than 200. In view of the vast number of primary amines and aliphatic halides which are known and/or can be synthesized by conventional procedures and since the substituent represented by R is not critical, no further elaboration on the groups represented by R is warranted. However, it is preferred that substituent R be devoid of amino groups, including unsubstituted and substituted amino groups, since such groups can affect detrimentally the synthesis of the azo compounds. The substituents described above in the definition of R² are typical of the groups which R can represent.

The couplers used in the synthesis of our novel azo compounds can be prepared by procedures well known in the art or by techniques analogous thereto. The specific groups encompassed by the generic language appearing in the definitions of A, R¹, R² and R³ are well known or are chemically equivalent to groups disclosed in the prior art pertaining to disperse azo dyes. As used herein to describe a group containing an alkyl moiety, "lower" designates a carbon content of one to about four carbon atoms. Each aryl moiety of the aryl- and arylene-containing groups, e.g., aroyloxy, phthalimido, arylthio, etc., which our compounds can contain preferably is phenyl, phenylene, and phenyl and phenylene substituted with lower alkyl, lower alkoxy, lower alkoxycarbonyl or halogen such as a chlorine or bromine atom.

The organic acyl radicals represented by A preferably are formyl, lower alkanoyl, aroyl, cyclohexylcarbonyl, lower alkoxycarbonyl, aryloxycarbonyl, lower alkylsulfonyl, cyclohexylsulfonyl, arylsulfonyl, carbamoyl, lower alkylcarbamoyl, arylcarbamoyl, furoyl, etc. The alkanoyl groups can be substituted with substituents such as halogen, aryl, cyano, lower alkoxy, aryloxy, benzyloxy, lower alkylthio, lower alkylsulfonyl, etc. The alkylsulfonyl groups also can be substituted, for example, with cyano, hydroxy, halogen and the like. The alkoxycarbonyl groups can be substituted, for example, with hydroxy, alkoxy and cyano. Acetyl, propionyl, butyryl, cyanoacetyl, chloroacetyl, trifluoroacetyl, phenylacetyl, methoxyacetyl, methylthioacetyl, methylsulfonylacetyl, methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, 2cyanoethylsulfonyl, 2-hydroxyethylsulfonyl, and 2-chloroethylsulfonyl, are examples of the alkanoyl, alkoxycarbonyl and alkylsulfonyl groups which A can represent. Dimethylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, butylcarbamoyl, phenylcarbamoyl and dimethylcarbamoyl are examples of the substituted carbamoyl groups. The unsubstituted and substituted alkanoyl, aroyl and alkoxycarbonyl groups are preferred.

The substituted alkyl groups represented by R² preferably are arylmethyl, arylethyl, cyclohexylmethyl, 2-cyanoethyl, or a group having the formula --Z--R⁹ in which Z is ethylene, propylene, trimethylene, or tetramethylene and R⁹ is any of the substituents, except aryl, cyano, and cyclohexyl, which can be present on the substituted alkyl groups represented by R² as defined above. Similarly, the preferred substituted alkyl groups represented by R³ are arylmethyl, arylethyl, cyclohexylmethyl or a group having the formula --Z--R¹⁰ in which Z is defined above and R¹⁰ is any of the substituents, except aryl and cyclohexyl, which can be present on the substituted alkyl groups which R³ can represent according to the above definitions thereof. It is also preferred that one of R¹ and R³ is hydrogen.

A group of our compounds which are especially preferred because of their cost:performance ratio are those having the formula ##STR5## wherein R is lower alkyl; arylmethyl; cyclohexylmethyl; 2-cyanoethyl; 2-carbamoylethyl; aryl; cyclohexyl; or the group --Z--R¹¹ in which Z is ethylene, propylene, or trimethylene and R¹¹ is succinimido, glutarimido, phthalimido, hydroxy, lower alkanoyloxy, 2-pyrrolidinono, or lower alkoxy;

A is lower alkanoyl, benzamido or lower alkoxycarbonyl;

R¹ is hydrogen or when R³ is hydrogen, R¹ is methyl;

R² is lower alkyl; allyl; cyclohexyl; arylmethyl; cyclohexylmethyl; 2-cyanoethyl; 2-carbamoylethyl; N-lower alkyl-2-carbamoylethyl; N,N-di-lower alkyl-2-carbamoylethyl; or the group --Z--R¹² in which Z is ethylene, propylene or trimethylene and R¹² is lower alkanoyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, succinimido, glutarimido, phthalimido, aroyloxy, lower alkoxy or the group ##STR6## R³ is hydrogen; lower alkyl; cyclohexyl; arylmethyl; cyclohexylmethyl; or the group --Z--R¹³ in which Z is ethylene, propylene or trimethylene and R¹³ is lower alkanoyloxy, lower alkoxycarbonyl or lower alkoxycarbonyloxy;

in which each aryl moiety is phenyl, tolyl, anisyl, ethoxyphenyl or chlorophenyl. When R² and R³ both represent substituents conforming to the formulas --Z--R¹² and --Z--R¹³ the Z groups preferably are the same.

Our novel compounds and their synthesis and use are further illustrated by the following examples.

EXAMPLE 1

To 2-aminoethanol (12.2 g.) is added portionwise at 100°-125° C. 4-nitrophthalic anhydride (38.6 g.) with manual stirring. The mixture is heated gradually to 150° C. and kept at 150°-160° C. for 1 hr. with occasional stirring. The reaction mixture is cooled slightly and 50 ml. of ethanol is added. This solution is then drowned into 200 ml. of water. The product, N-(2-hydroxyethyl)-4-nitrophthalimide, is collected by filtration, washed with water and dried in air. It melts at 118°-119° C. and weighs 30.0 g.

EXAMPLE 2

N-(2-Hydroxyethyl)-4-nitrophthalimide (30.0 g.), ethanol (300 ml.), and Raney nickel (3.0 g.) are mixed and hydrogenated at 100° C. and 1500 psi. until hydrogen uptake ceases. The hot solution is filtered to remove the Raney nickel and the solvent evaporated to yield 4-amino-N-(2-hydroxyethyl)-phthalimide, the amine which melts at 171°-173° C.

EXAMPLE 3

A mixture of 4-nitrophthalimide (38.4 g.), iodoethane (46.8 g.), potassium carbonate (27.6 g.), and N,N-dimethylformamide (200 ml.) are heated and stirred at 95°-100° C. for 2 hr. An additional amount of iodoethane (46.8 g.) is added and the reaction mixture heated 4 hr. longer at 95°-100° C. The reaction mixture is drowned into 1500 ml. of water. The product, N-ethyl-4-nitrophthalimide, is collected by filtration, washed with water and recrystallized from methanol. It melts at 113°-114° C.

EXAMPLE 4

N-Ethyl-4-nitrophthalimide (28.0 g.) is hydrogenated in 400 ml. of ethanol and in the presence of Raney nickel catalyst (10 g.) at 100° C. and 1500 psi. pressure. The reaction mixture is filtered to remove the catalyst and the filtrate is concentrated to yield the product, 4-amino-N-ethylphthalimide, which is recrystallized from methanol-water mixture. It melts at 169°-171° C.

EXAMPLE 5

3-Nitrophthalimide (30.0 g.) is ethylated with iodoethane in the same manner as the 4-nitro isomer (Example 3) to yield 35.4 g. of N-ethyl-3-nitrophthalimide melting at 102°-103° C.

EXAMPLE 6

N-Ethyl-nitrophthalimide (35.4 g.) is hydrogenated as in Example 4 to yield 22.5 g. of 3-amino-N-ethylphthalimide which melts at 134°-136° C.

EXAMPLES 7-14

Sodium nitrite (2.88 g.) is added gradually to 20 ml. of conc. H₂ SO₄. The solution is cooled and 1:5 acid (1 part by volume propionic acid to 5 parts by volume acetic acid) (40 ml.) is added below 15° C. To this mixture is added 4-amino-N-ethylphthalimide (7.6 g., 0.04 mole), followed by 40 ml. of 1:5 acid, all below 5° C. The reaction mixture is stirred at 0°-5° C. for 2 hr. The following couplers (0.005 mole) are dissolved in 25 ml. of 1:5 acid:

N,n-diethyl-m-acetamidoaniline (Example 7)

N-ethyl-N-n-propyl-m-acetamidoaniline (Example 8)

N-β-acetoxyethyl-N-ethyl-m-acetamidoaniline (Example 9)

N,n-di-β-acetoxyethyl-m-acetamidoaniline (Example 10)

N-β-cyanoethyl-N-ethyl-m-acetamidoaniline (Example 11)

N-ethyl-N-β-succinimidoethyl-m-acetamidoaniline (Example 12)

N-benzyl-N-ethyl-m-acetamidoaniline (Example 13)

N-β-acetoxyethyl-N-cyclohexyl-m-acetamidoaniline (Example 14)

To each chilled coupler solution is added a 0.005 mole aliquot of diazonium salt solution. The coupling mixtures are buffered by the addition of ammonium acetate and allowed to stand for 1 hr. The azo compound products are precipitated by the addition of water, collected by filtration, washed with water and dried in air. If needed, the azo products are purified by slurrying in hot methanol, cooling, filtering and washing with methanol.

The azo compounds set forth in the following table are prepared according to the synthesis techniques described herein and conform to formula (I). The structure of each of the azo compounds prepared in Examples 7-14, and the approximate shade each produces on polyester, polyamide and cellulose ester fibers, is indicated by Examples 7-14 of the Table. The phthalimidyl diazo component of the compounds of Examples 7-128 is bonded to the azo group at the 4-position, whereas the diazo component of the compounds of Examples 129-185 is bonded to the azo group at the 3-position.

                                      TABLE                                        __________________________________________________________________________     Ex-                                                                            ample                                                                          No. R           A         R.sup.1                                                                            R.sup.2         R.sup.3      Color               __________________________________________________________________________      7  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 8   --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            CH.sub.3     Red                 9   --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                --C.sub.2 H.sub.5                                                                           Scarlet             10  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Orange              11  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 CN                                                                         --C.sub.2 H.sub.5                                                                           Red                 12  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H                                                                                   ##STR7##       --C.sub.2 H.sub.5                                                                           Scarlet             13  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub. 2 C.sub.6 H.sub.5                                                                    --C.sub.2 H.sub.5                                                                           Scarlet             14  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.6 H.sub.11                                                                             --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             15  H           --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            CH.sub.3     Red                 16  H           --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             17  --(CH.sub.2).sub.3 CH.sub.3                                                                --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             18  --(CH.sub.2).sub.3 CH.sub.3                                                                --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             19  --(CH.sub.2).sub.3 CH.sub.3                                                                --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 C.sub.6 H.sub.5                                                                  Scarlet             20  --(CH.sub.2).sub.3 CH.sub.3                                                                --COCH.sub.3                                                                             H                                                                                   ##STR8##       --C.sub.2 H.sub.5                                                                           Scarlet             21  --CH.sub.2 C.sub.6 H.sub.5                                                                 -- COCH.sub.3                                                                            H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             22  --CH.sub.2 C.sub.6 H.sub.5                                                                 --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Orange              23  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH(CH.sub.3)OOCCH                                                   .sub.3       Scarlet             24  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 CONH.sub.2                                                                 --C.sub.2 H.sub.5                                                                           Scarlet             25  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.6 H.sub.11                                                                             --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Red                 26  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH=CH.sub.2                                                                      Red                 27  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                               --C.sub.2 H.sub.5                                                                           Red                 28  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 NHCOC.sub.6 H.sub.5                                                        --C.sub.2 H.sub.5                                                                           Red                 29  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 NHCOOC.sub.2 H.sub.5                                                       --C.sub.2 H.sub.5                                                                           Red                 30  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.5                                                                     --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             31  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.11                                                                    --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Red                 32  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             --CH.sub.3                                                                         --C.sub.2 H.sub.5                                                                              H            Scarlet             33  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             --CH.sub.3                                                                         --CH(CH.sub.3)C.sub.2 H.sub.5                                                                  H            Scarlet             34  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             --CH.sub.3                                                                         --C.sub.6 H.sub.11                                                                             H            Scarlet             35  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             --CH.sub.3                                                                         --CH.sub.2 C.sub.6 H.sub.5                                                                     H            Scarlet             36  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             --CH.sub.3                                                                         --CH.sub.2 CH.sub.2 CN                                                                         H            Orange              37  --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             --CH.sub.3                                                                         --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                H            Orange              38  --CH.sub.2 C.sub. 6 H.sub.11                                                               --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             39  --CH.sub.2 C.sub.6 H.sub.11                                                                --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            CH.sub.3     Scarlet             40  --C.sub.6 H.sub.11                                                                         --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            CH.sub.3     Scarlet             41  --C.sub.6 H.sub.11                                                                         --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             42  --C.sub.6 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             43  --C.sub.6 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.6 H.sub.11                                                                             --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Red                 44  --C.sub.6 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.11                                                                    --C.sub.2 H.sub.5                                                                           Scarlet             45  --(CH.sub.3).sub.3 OCH.sub.3                                                               --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 46  --(CH.sub.3).sub.3 OCH.sub.3                                                               -- COCH.sub.3                                                                            H                                                                                   ##STR9##       --C.sub.2 H.sub.5                                                                           Scarlet             47  --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                            --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 CH.sub.3                                                                   --C.sub.2 H.sub.5                                                                           Red                 48  --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                            --COCH.sub.3                                                                             H   --C.sub.6 H.sub.11                                                                             --CH.sub.2 CH.sub.2                                                            CH.sub.3     Red                 49  --CH.sub.2 CH.sub.2 OH                                                                     --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            CH.sub.3     Red                 50                                                                                  ##STR10##  --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            CH.sub.3     Red                 51                                                                                  ##STR11##  --COCH.sub.3                                                                             H   --C.sub.6 H.sub.11                                                                             --C.sub.2 H.sub.5                                                                           Red                 52  --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                           --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            CH.sub.3     Red                 53  -- CH.sub.2 C.sub.6 H.sub.4 -p--OCH.sub.3                                                  --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             54  --CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                        --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             55  --CH.sub.2 CH.sub.2 CONH.sub.2                                                             --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             56  --CH.sub.2 CH.sub.2 CN                                                                     --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             57                                                                                  ##STR12##  --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 58  --CH.sub.2 CH.sub.2 Cl                                                                     --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 59  --CH.sub.2 CH.sub.2 SO.sub.2 C.sub.6 H.sub.5                                               --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 60  --CH.sub.2 CH.sub.2 NHSO.sub.2 CH.sub.3                                                    --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 61  --CH.sub.2 CH.sub.2 N(CH.sub.3)SO.sub.2 CH.sub.3                                           --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 62                                                                                  ##STR13##  --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 63                                                                                  ##STR14##  --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             64  --C.sub.6 H.sub.4 -m--CH.sub.3                                                             --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             65  --C.sub.6 H.sub.4 -m--Cl                                                                   --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             66  --C.sub.6 H.sub.4 -p--OCH.sub.3                                                            --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             67   --CH.sub.2 CH.sub.2 COOCH.sub.3                                                           --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Scarlet             68                                                                                  ##STR15##  --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 69                                                                                  ##STR16##  --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 70  --CH.sub.2 CH.sub.2 OOCC.sub.6 H.sub.5                                                     --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 71  --CH.sub.2 CH.sub.2 OOCOC.sub.2 H.sub.5                                                    --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 72  --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                  --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 73                                                                                  ##STR17##  --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 74                                                                                  ##STR18##  --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 75                                                                                  ##STR19##  --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 76  --CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                                       --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 77  --CH.sub.2 --C.sub.6 H.sub.4-                                                              --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 p--COOCH.sub.3                                                                 78  --CH.sub.2 CH= CH.sub.2                                                                    --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 79  --CH(CH.sub.3)C.sub.2 H.sub.5                                                              --COC.sub.2 H.sub.5                                                                      H   -- C.sub.2 H.sub.5                                                                             --C.sub.2 H.sub.5                                                                           Red                 80  --CH.sub.2 COC.sub.6 H.sub.5                                                               --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 81  --C.sub.6 H.sub.4 -p--SO.sub.2 CH.sub.3                                                    --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 82  --C.sub.6 H.sub.4 -p--NHCOCH.sub.3                                                         --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 83  --CH.sub.2 C.sub.6 H.sub.10-                                                               --COC.sub.2 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 p--CH.sub.2 OH                                                                 84  --C.sub.2 H.sub.5                                                                          --COOC.sub.2 H.sub.5                                                                     H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 85  --C.sub.2 H.sub.5                                                                          --COOC.sub.2 H.sub.5                                                                     H   --CH.sub.2 C.sub.6 H.sub.5                                                                     --CH.sub.2 C.sub.6 H.sub.5                                                                  Scarlet             86  --C.sub.2 H.sub.5                                                                          --COC.sub.6 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 87  --C.sub.2 H.sub. 5                                                                         --COC.sub.6 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Red                 88  --C.sub.2 H.sub.5                                                                          --COC.sub.6 H.sub.11                                                                     H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Red                 89  --C.sub.2 H.sub.5                                                                          --COC.sub.6 H.sub.5                                                                      CH.sub.3                                                                           H               --CH.sub.2 (CH.sub.3)C.sub.2                                                    H.sub.5     Red                 90  --C.sub.2 H.sub.5                                                                          --COCH.sub.2 OH                                                                          H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 91  --C.sub.2 H.sub.5                                                                          --COCH.sub.2 Cl                                                                          H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 92  --C.sub.2 H.sub.5                                                                          --COCH.sub.2 OCH.sub.3                                                                   H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 93  --C.sub.2 H.sub.5                                                                          --COCH.sub.2 CH.sub.2 Cl                                                                 H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 94  --C.sub.2 H.sub.5                                                                          --COCH.sub.2 OC.sub.6 H.sub.5                                                            H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 95  --C.sub.2 H.sub.5                                                                          -- COCH.sub.2 C.sub.6 H.sub.5                                                            H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 96  --C.sub.2 H.sub.5                                                                          --SO.sub.2 CH.sub.3                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 97  --C.sub.2 H.sub.5                                                                          --COCH.sub.2 CH.sub.2 CN                                                                 H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 98  --C.sub.2 H.sub.5                                                                          --CONHC.sub.2 H.sub.5                                                                    H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 99  --C.sub.2 H.sub.5                                                                          --CONHC.sub.6 H.sub.5                                                                    H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 100 --C.sub.2 H.sub.5                                                                          --COCH.sub.2 OOCCH.sub.3                                                                 H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Red                 101 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H                                                                                   ##STR20##      --C.sub.2 H.sub.5                                                                           Scarlet             102 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H                                                                                   ##STR21##      --C.sub.2                                                                                   Scarlet             103 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 N(CH.sub.3)SO.sub.2                                        CH.sub.3        --C.sub.2 H.sub.5                                                                           Scarlet             104 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5)SO.sub                                   .2 C.sub.6 H.sub.5                                                                             --C.sub.2 H.sub.5                                                                           Scarlet             105 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H                                                                                   ##STR22##      --C.sub.2 H.sub.5                                                                           Scarlet             106 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 NH(C.sub.6 H.sub.5)SO.su                                   b.2 CH.sub.3    --C.sub.2 H.sub.5                                                                           Scarlet             107 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 --SO.sub.2 --CH.sub.2                                      CH.sub.2 --                  Orange              108 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                                      Scarlet             109 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --(CH.sub.2).sub.5 --        Red                 110 --C.sub.2 H.sub. 5                                                                         --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 N(SO.sub.2 CH.sub.3)CH.s                                   ub.2 CH.sub.2 --             Scarlet             111 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 --C.sub.6 H.sub.4 -p--COOCH.sub.3                                                   --C.sub.2 H.sub.5                                                                           Scarlet             112 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH(OOCH.sub.3)CH.sub.2 OOCH.sub.3                                                   --C.sub.2 H.sub.5                                                                           Scarlet             113 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH(OOCH.sub.3)CH.sub.2 Cl                                                           --C.sub.2 H.sub.5                                                                           Scarlet             114 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           --C.sub.2 H.sub.5                                                                           Scarlet             115 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCC.sub.6 H.sub.5                                                         --C.sub.2 H.sub.5                                                                           Scarlet             116 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.2 OC.sub.6                                       H.sub.5         --C.sub.2 H.sub.5                                                                           Scarlet             117 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.2 C.sub.6                                        H.sub.5         --C.sub.2 H.sub.5                                                                           Scarlet             118 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCH.sub.2 COCH.sub.3                                                      --C.sub.2 H.sub.5                                                                           Scarlet             119 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.2 CN                                                             --C.sub.2 H.sub.5                                                                           Scarlet             120 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.2 CH.sub.2                                       OCH.sub.3       --C.sub.2 H.sub.5                                                                           Scarlet             121 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.2 CH.sub.2                                       COOC.sub.2 H.sub.5                                                                             --C.sub.2 H.sub.5                                                                           Scarlet             122 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.5                                                                     --CH.sub.2 C.sub.6 H.sub.4                                                     -p--COOCH.sub.3                                                                             Orange              123 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.11                                                                    --CH.sub.2 C.sub.6 H.sub.4                                                     -p--COOCH.sub.3                                                                             Orange              124 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.5                                                                     --C.sub.6 H.sub.11                                                                          Scarlet             125 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.11                                                                    --CH.sub.2 C.sub.6 H.sub.11                                                                 Red                 126 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.11                                                                    --CH.sub.2 CH.sub.2                                                            CONHCH(CH.sub.3).sub.2                                                                      Red                 127 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.6 H.sub.11                                                                             --CH.sub.2 CH.sub.2                                                            OOCOC.sub.2 H.sub.5                                                                         Red                 128 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.6 H.sub.11                                                                             --CH.sub.2 CH.sub.2                                                                         Red                 129 --C.sub.2 H.sub.5                                                                          --NHCOCH.sub.3                                                                           H   --C.sub.2 H.sub.5                                                                              --CH.sub.2 CH.sub.2                                                            CH.sub.3     Scarlet             130 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.6 H.sub.11                                                                             --C.sub.2 H.sub.5                                                                           Scarlet             131 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.5                                                                     --C.sub.2 H.sub.5                                                                           Orange              132 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                --C.sub.2 H.sub.5                                                                           Orange              133 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H                                                                                   ##STR23##      --C.sub.2 H.sub.5                                                                           Orange              134 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Orange              135 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH(C.sub.2 H.sub.5)(CH.sub.2).sub                                   .3 CH.sub.3     --C.sub.2 H.sub.5                                                                           Scarlet             136 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 NHCOCH.sub.3                                                               --C.sub.2 H.sub.5                                                                           Scarlet             137 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             --CH.sub.3                                                                         --C.sub.2 H.sub.5                                                                              H            Orange              138 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             --CH.sub.3                                                                         --CH.sub.2 C.sub.6 H.sub.5                                                                     H            Orange              139 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             --CH.sub.3                                                                         --C.sub.6 H.sub.11                                                                             H            Orange              140 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCC.sub.6 H.sub.5                                                         --(CH.sub.2).sub.3 CH.sub.3                                                                 Orange              141 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCOC.sub.2 H.sub.5                                                        --CH.sub.2 CH(CH.sub.3).sub.                                                   2            Orange              142 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.6 H.sub.11                                                                             --CH.sub.2 CH(OOCCH.sub.3)CH                                                   .sub.3       Scarlet             143 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --C.sub.6 H.sub.11                                                                             --CH.sub.2 C.sub.6 H.sub.5                                                                  Scarlet             144 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH(OOCCH.sub.3)CH.sub.2 OOCCH.sub                                   .3              --C.sub.2 H.sub.5                                                                           Orange              145 --C.sub.2 H.sub.5                                                                          --COC.sub.6 H.sub.5                                                                      --CH.sub.3                                                                         --CH(CH.sub.3)C.sub.2 H.sub.5                                                                  H            Orange              146 --C.sub.2 H.sub.5                                                                          --COC.sub.2 H.sub.5                                                                      H   --CH.sub.2 CH(CH.sub.3).sub.2                                                                  --CH.sub.2 CH.sub.2                                                            CH.sub.3     Scarlet             147 --C.sub.2 H.sub.5                                                                          --COC.sub.2 H.sub.5                                                                      H   --CH.sub.2 C.sub.6 H.sub.4 -p--COOCH.sub.3                                                     --CH.sub.2 CH.sub.2                                                            CH.sub.3     Orange              148 --C.sub.2 H.sub.5                                                                          --COC.sub.2 H.sub.5                                                                      H   --CH.sub.2 C.sub.6 H.sub.11                                                                    --CH.sub.2 CH.sub.2                                                            OOCH.sub.3   Orange              149 --C.sub.2 H.sub.5                                                                          --COC.sub.2 H.sub.5                                                                      H   --CH.sub.2 CH.sub.2 CN                                                                         --C.sub.2 H.sub.5                                                                           Orange              150 --C.sub.2 H.sub.5                                                                          --COC.sub.2 H.sub.5                                                                      H   --CH.sub.2 CH.sub.2 CONH.sub.2                                                                 --C.sub.2 H.sub.5                                                                           Orange              151 --C.sub.2 H.sub.5                                                                          --COC.sub.2 H.sub.5                                                                      H   --CH.sub.2 CH.sub.2 CONHCH(CH.sub.3).sub.2                                                     --C.sub.2 H.sub.5                                                                           Orange              152 --C.sub.2 H.sub.5                                                                          --COC.sub.2 H.sub.5                                                                      H   --CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5                                                           --C.sub.2 H.sub.5                                                                           Orange              153 --CH(CH.sub.3).sub.2                                                                       --COCH(CH.sub.3).sub.2                                                                   H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             154 --(CH.sub.2).sub.3 CH.sub.3                                                                --COOC.sub.2 H.sub.5                                                                     H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             155 --CH.sub.2 C.sub.6 H.sub.5                                                                 --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             156 --C.sub.6 H.sub.11                                                                         --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             157 --(CH.sub.3).sub.3 OCH.sub.3                                                               --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             158 --CH.sub.2 CH.sub. 2 OH                                                                    --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             159 --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                            --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             160                                                                                 ##STR24##  --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             161 --CH.sub.2 CH.sub.2 C.sub.6 H.sub.4-                                                       --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             p--COOCH.sub.3                                                                 162 H           --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             163                                                                                 ##STR25##  --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             164 --CH.sub.2 CH=CH.sub.2                                                                     --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             165 --CH.sub.2 CH(C.sub.2 H.sub.5)                                                             --COCH.sub.2 OH                                                                          H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet                 (CH.sub.2).sub.3 CH.sub.3                                                  166 --CH.sub.2 CH.sub.2 CH.sub.3                                                               --COC.sub.6 H.sub.5                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             167 --CH.sub.2 CH(CH.sub.3).sub.2                                                              --COC.sub.6 H.sub.11                                                                     H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             168 --CH.sub.2 CH(CH.sub.3).sub.2                                                              --COCH.sub.2 OC.sub.6 H.sub.5                                                            H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             169 --CH.sub.2 CH(CH.sub.3).sub.2                                                              --COC.sub.6 H.sub.4-                                                                     H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             p--COOCH.sub.3                                                                 170 --CH.sub.2 CH(CH.sub.3).sub.2                                                              --SO.sub.2 CH.sub.3                                                                      H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             171 --CH.sub.2 CH(CH.sub.3).sub.2                                                              --CONHC.sub.2 H.sub.5                                                                    H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             172 --CH.sub.2 C.sub.6 H.sub.4 -p--Cl                                                          --COOC.sub.2 H.sub.5                                                                     H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             173 --C.sub.6 H.sub.4 -p--OCH.sub.3                                                            -- COCH.sub.2 CH.sub.2 OH                                                                H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             174 --C.sub.6 H.sub.4 -m--CH.sub.3                                                             --COCH.sub.2 Cl                                                                          H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             175 --C.sub.6 H.sub.4-                                                                         --COCH.sub.3                                                                             H   --C.sub.2 H.sub.5                                                                              --C.sub.2 H.sub.5                                                                           Scarlet             p--NHCOCH.sub.3                                                                176 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 CN                                                                         --(CH.sub.2).sub.3 OOCCH.sub                                                   .3           Orange              177 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OOCCH.sub.3                                                                --CH.sub.2 CH.sub.2                                                            OOCCH.sub.3  Orange              178 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2                                          CH.sub.2 --                  Orange              179 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                                                      Orange              180 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH(OOCCH.sub.3)CH.sub.2 Cl                                                          --C.sub.2 H.sub.5                                                                           Orange              181 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                            --C.sub.2 H.sub.5                                                                           Scarlet             182 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.11                                                                    --C.sub.2 H.sub.5                                                                           Scarlet             183 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.5                                                                     --CH.sub.2 C.sub.6 H.sub.5                                                                  Scarlet             184 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.11                                                                    --CH.sub.2 C.sub.6 H.sub.5                                                                  Scarlet             185 --C.sub.2 H.sub.5                                                                          --COCH.sub.3                                                                             H   --CH.sub.2 C.sub.6 H.sub.10 -p--CH.sub.3                                                       --CH.sub.2 CH.sub.2                                                            CH.sub.3     Scarlet             __________________________________________________________________________

The compounds of the invention can be applied to polyester by known disperse dyeing techniques employing carriers, surfactants, dispersing agents, etc. Dyeing can be conducted at atmospheric or superatmospheric pressures. The following example illustrates a dyeing procedure for applying the azo compounds of the invention to dye polyester textile materials at atmospheric pressure and at the boil:

EXAMPLE 186

An amount of 0.1 g. of the azo compound of Example 8 is dissolved in 10 cc. of 2-methoxyethanol. A small amount (3 to 5 cc.) of a 3% sodium lignin sulfonate aqueous solution is added, with stirring, and then the volume of the bath is brought to 300 cc. with water. 3 cc. of a chlorinated benzene emulsion carrier (Tanavol) is added to the bath and 10.0 g. of a textile fabric made of poly(ethylene terephthalate) fibers is placed in the bath and worked 10 min. without heat. The dyeing is carried out at the boil for 1 hr. The dyed fabric is removed from the dyebath and scoured for 20 min. at 80° C. in a solution containing 1 g./l. neutral soap and 1 g./l. sodium carbonate. The fabric is then rinsed, dried in an oven at 250° F. and heat set (for the removal of residual carrier) for 5 min. at 350° F. The fabric is dyed a bright shade of red and exhibits excellent fastness properties when tested according to conventional methods such as those described in the Technical Manual of the American Association of Textile Chemists and Colorists, 1968 edition.

The following example describes a method by which our compounds can be applied to texturized polyester fibers:

EXAMPLE 187

The azo compound of Example 12 (66.7 mg.) is dissolved/dispersed in 10 cc. of 2-methoxyethanol in a Launder-Ometer container to which is then added with stirring about 0.2 g. sodium lignin sulfonate and 0.2 g. of a surfactant (Igepon T-51) from a stock solution containing both components. The volume of the bath is brought to 300 ml. with water and 0.3 g. of a butyl benzoate emulsion carrier (DAC-888) is added. A fabric (10 g.) of texturized poly(ethylene terephthalate) fibers is wet out and placed in the bath which is then sealed and affixed to the rotating arm of a Launder-Ometer set at 120° F. After placing the container-bath in rotation the Launder-Ometer is set at 260° F. and after the heating medium reaches that temperature, dyeing with rotation is continued for 11/2 hours. After allowing the container-bath to cool, the dyed fabric is removed, rinsed with water and dried. If necessary, residual carrier can be removed by heat setting as described in the preceding example.

The compounds of the invention can also be applied to polyester textile materials by the heat fixation technique described in U.S. Pat. No. 2,663,612 and in the American Dyestuff Reporter, 42, 1 (1953). The following procedure describes how the azo compounds of the invention can be applied to polyester materials by the heat fixation technique:

EXAMPLE 188

A mixture of 500 mg. of the compound of Example 10, 150 mg. of a sodium lignosulfonate dispersing agent (Marasperse N), 150 mg. of a partially desulfonated sodium lignosulfonate (Marasperse CB), 0.5 ml. glycerin, and 1.0 ml. of water is ground in a micro-size container (an accessory for a 1-quart size Szegvari Attritor) for approximately 3.5 hrs. Enough 1/8-inch stainless steel balls are added to provide maximum grinding. When the grinding is complete, the entire contents are poured into a beaker and 100 ml. of water are used to wash the remaining dye paste from the micro-container. The dye paste is then heated slowly to 65° C. with continuous stirring. A thickener and penetrating mixture is prepared by mixing

1 ml. of a complex diaryl sulfonate surfactant, (Compound 8-S),

3 ml. of a 3% solution of a sodium N-methyl-N-oleoyltaurate (Igepon T-Sl),

8 ml. of a 25% solution of natural gums (Superclear 80N),

and sufficient water to bring the volume to 100 ml. The thickener and penetrating mixture is added to the dye paste, the volume is adjusted to 200 ml. and the mixture is agitated for 15 min. The dye mixture is then filtered through cheesecloth to remove the stainless steel balls and added to the reservoir of a Butterworth padder where it is heated to about 45° to 60° C. 10 g. of a fabric of poly(ethylene terephthalate) fibers and 10 g. of a fabric of 65/35 spun poly(ethylene terephthalate)/cotton fibers are sewn together, end-to-end, and padded for 5 min. of continuous cycling through the dye mixture and between three rubber squeeze rollers of the padder. Dye mixture pick-up is about 60% based on the weight of the fabrics. The padded fabrics are dried at 200° F. and then heat-fixed for 2 min. at 415° F. in a forced air oven. The dyed fabrics are scoured for 20 min. at 65° to 70° C. in a solution containing 0.2% sodium hydrosulfite, 0.2% sodium carbonate and 1.7% of a 3% solution of sodium N-methyl-N-oleoyltaurate and then dried. The dyed fabrics possess excellent brightness and fastness to light and sublimation.

The heat fixation dyeing procedure described above can be varied by the substitution of other dispersing agents, surfactants, suspending agents, thickeners, etc. The temperature and time of the heat-fixation step can also be varied.

Fibers having a basis of a linear terephthalate polyester and sold under the trademarks "Kodel", "Dacron", "Fortrel", "Vycron" and "Terylene" are illustrative of the linear aromatic polyester textile materials that can be dyed with the novel azo compounds. Polyesters prepared from ethylene glycol and dimethylterephthalate and cyclohexanedimethanol and dimethylterephthalate are examples of such linear aromatic polyesters. Polyesters prepared from cyclohexanedimethanol and dimethylterephthalate are more particularly described in U.S. Pat. No. 2,901,466. Poly(ethylene terephthalate) polyester fibers are described, for example, in U.S. Pat. No. 2,465,319. The polymeric linear polyester materials disclosed in U.S. Pat. Nos. 2,945,010; 2,957,745 and 2,989,363, for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 0.35 and preferably, about 0.6. The inherent viscosity of the poly(1,4-cyclohexylenedimethylene terephthalate) polymer is also at least 0.35. These inherent viscosities are measured at 25° C. using 0.25 g. polymer per 100 ml. of a solvent consisting of 60% phenol and 40% tetrachloroethane. The polyester fabrics, yarns, fibers and filaments that are dyed with the novel azo compounds can also contain minor amounts of other additives such as brighteners, pigments, delusterants, inhibitors, stabilizers, etc.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. 

We claim:
 1. A compound having the formula ##STR26## wherein R and R² are the same or different and each is alkyl containing one to eight carbon atoms; cyclohexyl; cyclohexyl substituted with lower alkyl; arylmethyl; arylethyl; cyclohexylmethyl; 2-cyanoethyl or a group having the formula --Z--R⁹ in which Z is ethylene, propylene, trimethylene or tetramethylene and R⁹ is lower alkoxy, aryloxy, lower alkanoyloxy, lower alkoxycarbonyl, lower alkoxycarbonyloxy, aroyloxy or ##STR27## wherein R⁴ individually is hydrogen, lower alkyl or aryl;R⁵ individually is hydrogen or lower alkyl; R⁴ and R⁵ taken together are --(CH₂)₅ -- or --CH₂ CH₂ OCH₂ CH₂ --; R⁶ is hydrogen, lower alkyl, aryl, or cyclohexyl; R⁷ is ethylene, propylene, trimethylene, o-cyclohexylene, or o-arylene; X is --CH₂ --, --CO--, or --SO₂ --; and R⁸ is aryl, benzyl, cyclohexyl, 1,2,4-triazol-3-yl, or 2-benzothiazolyl; A is lower alkanoyl; lower alkanoyl substituted with chlorine, bromine, aryl, cyano, lower alkoxy, benzyloxy, lower alkylthio, aryloxy or lower alkylsulfonyl; lower alkoxycarbonyl; or aroyl; R¹ is hydrogen or methyl, one of R¹ and R³ being hydrogen; R³ is hydrogen, lower alkyl, arylmethyl, arylethyl, allyl, aryl, or a group having the formula --Z--R¹⁰ in which Z is ethylene, propylene, trimethylene, or tetramethylene and R¹⁰ is lower alkoxy, aryloxy, lower alkanoyloxy, lower alkoxycarbonyl, or lower alkoxycarbonyloxy.
 2. A compound according to claim 1 wherein R is lower alkyl; A is acetyl or propionyl; R¹ is hydrogen; R² is benzyl and R³ is ethyl or propyl. 